Reaction Chemistry & Engineering
Enhanced hydroformylation of 1-octene in n-butane expanded solvents with Co-based Complexes
Journal: Reaction Chemistry & Engineering
Manuscript ID RE-ART-02-2018-000034.R1
Article Type: Paper
Date Submitted by the Author: 30-Mar-2018
Complete List of Authors: Liu, Dupeng; University of Kansas, Chemical and Petroleum Engineering Xie, Zhuanzhuan; Center for Environmentally Beneficial Catalysis, Chemical and Petroleum Engineering Snavely, W.; University of Kansas, Center for Environmentally Beneficial Catalysis Chaudhari, Raghunath; University of Kansas, Chemical & Petroleum Engineering Subramaniam, Bala; University of Kansas, Center for Environmentally Beneficial Catalysis; University of Kansas, Chemical and Petroleum Engineering
Page 1 of 35 Reaction Chemistry & Engineering
Enhanced hydroformylation of 1-Octene in n-butane expanded
solvents with Co-based Complexes
Dupeng Liu,1,2 Zhuanzhuan Xie,2 William Kirk Snavely,2 Raghunath Chaudhari,1,2
and Bala Subramaniam1,2
1Department of Chemical & Petroleum Engineering, 2Center for Environmentally Beneficial Catalysis, University of Kansas Lawrence, KS 66047
Submitted to
Reaction Chemistry & Engineering
February 2018
1 Correspondence concerning this article should be addressed to B. Subramaniam at [email protected]
1 Reaction Chemistry & Engineering Page 2 of 35
Abstract
The use of n butane expanded liquids (BXLs) as reaction media to enhance
Co catalyzed hydroformylation of 1 octene has been successfully demonstrated.
Both 1 octene as well as typical hydroformylation mixtures are volumetrically expanded by n butane at typical hydroformylation conditions (~ 50% expansion at
1.8 MPa of n butane and 180 °C). By replacing up to 20% of the traditional solvent (toluene) in the reaction mixture with compressed n butane, the TOF for
Co catalyzed 1 octene hydroformylation with triphenylphosphine ligand was enhanced by approximately 20% in the BXL system. The higher TOF in BXLs is attributed to the improved syngas availability in the pressure tunable BXL phase compared to the traditional liquid phase. The main impediment to TOF enhancement is catalyst precipitation beyond a certain level of n butane dissolution in the liquid phase. Hence, catalyst complexes that show improved solubility in the BXL phase are desirable to better harness the potential benefits offered by gas